Thermofluid vehicles



United States Patent THERMOFLUID VEHICLES Lewis C. Hoffman, Scotch Plains, N.J., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Apr. 2, 1958, Ser. No. 725,785

16 Claims. (Cl. 106-230) This invention relates to new and improved thermofluid vehicles useful for the preparation of ceramic coating compositions.

The decoration of ceramic or metal surfaces with vitreous enamel coatings of any desired color is customarily carried out by the squeegeeing of a colored enamel coating composition, composed of a vehicle and a finely divided vitreous color enamel, through a screen stencil onto a ceramic or metal article and firing the coated article to fuse the enamel in the coating. In order that such decorating method may be carried out rapidly, the art has developed thermofiuid vehicles for such colored enamel compositions. Such thermofiuid vehicles melt at a temperature slightly above room temperature and freeze rapidly when the squeegeed paste contacts a ceramic or metal surface at about room temperature.

Thermofluid vehicles used in the art are of two general types, those comprised of a combination of a thermoplastic resin and a wax as exemplified in US. Patents Nos. 2,607,701, 2,607,702, and 2,682,480, or'those comprised of an all-wax medium as exemplified in US. Patents Nos. 2,617,740 and 2,823,138.

Although both types of thermofiuid vehicles are quite useful, they have not proven altogether satisfactory. As heretofore pointed out, there are so many required characteristics of a satisfactory vehicle for enamel coating compositions that to produce a completely suitable composition is very complicated. One of the outstanding objectionable characteristics of both types of previously known thermofiuid vehicles is the retention of screen markings on the fired enamel compositions. Thermofluid vehicles must retain a required stiffness or viscosity upon being submitted to enamel firing temperatures to prevent their running from the desired coating area. Consequently such enamel compositions will retain screen markings present as a result of their freezing upon contact with the relatively cold surface to be decorated.

It is an object of this invention to provide new and improved thermofiuid vehicles.

It is another object of this invention to provide thermofluid resin-wax and all-Wax vehicles for enamel coating compositions Which Will not run upon firing of the enamel coating compositions but will be smoothed out to eliminate any screen markings or other irregularities on the coating surfaces.

Other objects of the invention will appear hereinafter.

The objects of this invention may be accomplished by the addition, to a thermofiuid vehicle of either the resin-wax or all-wax type, of an anionic surface active agent comprising the alkaline reaction product of POC1 with a saturated aliphatic monohydroxy alcohol having 8 to 18 carbon atoms, or with a mixture of such an alcohol and an aliphatic glycol in which the carbon atoms to which the hydroxyl radicals are attached are separated by at least 4 carbon atoms. The addition to a thermofluid vehicle of between 0.5 and 15% by weight of the vehicle of such anionic surface active agent has been found to make the vitreous enamel color coating composition prepared with such vehicle self-smoothing to 2,965,509 Patented Dec. 20. 1960 eliminate any screen marks or other coating roughness in the applied coating composition without imparting to the composition any tendency to run during firing of the coated article.

The anionic surface active agents of this invention may be prepared by reacting POCl with a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and neutralizing or preferably slightly alkalinizing the reaction product. For example, POCl may be reacted with octanol, decanol, lauryl, cetyl or stearyl alcohols and.

the reaction product neutralized with a slight excess of an alkaline material. The preferred alkaline materials are alkali metal hydroxides and amines, particularly tertiary aliphatic amines, for example, trimethylamine,

triethylamine or triethanolamine.

The anionic agents may also be prepared by reacting the POCl with a saturated monohydroxy aliphatic alcohol of 8 to 18 carbon atoms and a saturated aliphatic. glycol in which the carbon atoms to which the hydroxyl radicals are attached are separated by at least 4 carbon atoms, for example, 1,6 hexanediol, 2,2 diethyl-1,3-propanediol, triethylene glycol, tetraethylene glycol and polyethylene glyco-ls having a molecular Weight of up to 4000. The POCl may be reacted with a mixture of the said monohydroxy alcohols and glycols, or it may be reacted in turn with the alcohol or glycol and then with the glycol or alcohol.

The neutralization is preferably carried out with at least a small excess of the alkaline material to produce a pH of at least 8. If desired, the alkalinization may be carried out to a pH of 12, depending to some extent on the alkalinizing material used. The resultant neutral or alkaline POCl alcohol or POCl -alcohol-glycol surface active agent is then admixed with a thermofiuid vehicle in the proportion of 0.5% to 15% by weight of the vehicle.

The following examples illustrate a number of preferred procedures for obtaining suitable phosphate ester anionic agents for use in the present invention.

Example 1 To a mixture of 28.4 parts of 1,6 hexanediol and 34.5

parts of 3,3,5 trimethylhexanol-l is added 37.1 parts of POCl The mixture is heated to a temperature of 70 C. and maintained at this temperature until gas evolution ceases. When the reaction is complete, as evidenced by cessation of gas evolution, the straw-colored viscous oil is allowed to cool to room temperature and then alkalinized by the addition thereto of parts of triethanolamine to produce the desired anionic phosphate ester surface active agent.

Example 2 70 parts of 3,3,5 trimethylhexanol-l is added to 30 parts of POCl The mixture is heated to approximately 70 C. at which temperature the reaction takes place until gas evolution ceases. The resultant material is allowed to cool to room temperature and is then neutralized by the addition of 100 parts of triethanolamine to produce a phosphate ester anionic surface active agent suitable for use in accordance with the invention.

amp e 30 parts of Carbowax 200, a polyethylene glycol sold by Carbide and Carbon Chemicals Corporation, having an-average molecular weight of-about 200, was mixed with 4'5 parts of decanol. 25 parts of POCl was {then added and th e mixture heated to a temperature of "about 70 C. and maintained at this temperature until cessation of gasevolution. The resultant product was then cooled tobbtain suitable phosphate ester anionic surface active agents for use in the present invention.

Example Glycol Alcohol P001 Alkalinlred Number parts 70 parts cetyl 30 100 parts trialcohol. eth anolanine. 17 parts 1.6 51 parts lauryl 32 Do. hexanediol. alcohol. 10 parts "Car- 55 parts stea- 35 10 parts 46% bowax 1000. ryl alcohol. NaOH. 10 parts Car- 65 parts cetyl 25 Do. bowax 750. alcohol. I L 70 parts 3,3,5 30 D0. trin ethylhexanol-l. 10 1 part 1,6 hexa 61 parts 3,3,5 38 Do.

nediol. trirr ethylhexanol-l. l1 18 parts 1,6 hex- 59 parts nor- 23 100 parts trianediol. mal stearyl ethanolaalcohol. mine.

Finely divided vitreous enamel is normally agglornof melting during firing of a thermofluid decoration, they will tend to level out the mesh marks in the print proportional to the extent of dispersion present. I accomplish this dispersion by the addition to the thermofluid vehicle of, an anionic surface active agent of the type hereinabove described. F

The amount of anionic agent for noticetable effect is 0.5%- to 1% of the vehicle. Most of the agents are liquids or soft solids and excessive amounts tend to cause reduction in solidification temperature of the vehicles. I have found about 5% to be optimum and 15% to be a safe maximum dependent, of course, on the physical nature of the; agent.

As shown in the patents above referred to, both the resin-wax and the all-wax types of vehicles are basically comprised of a fusible substance having a melting point of'between about 47 C. and 110 C. and having the property of rap'dly solidifying at room temperature. Such vehicles may also in some cases contain small amounts ofasolvent'for said resin or Wax and optionally small amounts of modifying substances.

"Resin-wax types of vehicles contain a thermoplastic resin in combination with a wax or wax-like material. As resins the vehIcle may contain rosin, abietic acid,

hydrogenated rosin, dimerized rosin, rosin esters, polyaeemoa desired characteristics of melting point, rapidity of hardeni'r'ig'fvlscosity, volatility during firing, and the like. "111' the case of all-wax types of} vehicles, the thermoplastic resins are omitted and the vehicle is basically composed of waxes, both natural and synthetic, and thickening waxlike materials such as "polyethylene glycols with wax solvents such as .satugated monohydroxy alcohols of 12 to 18 carbon atoms; 'm'onohydric carboxylic acids of 12 to 18' carbon atoms or parafliin wax having amelting point. of about 45' to 75 C.

Modifying agents such as soya lecithin, phosphorated tall oil or the like maybe added to impart resistance to molsture'condensa'tion', or urea or 'diphenyl to impart toughness to the coatings.

In preparing the colored vitreous enamel coating compositions, the above-described thermofluid vehicles are mixed with vitreous enamel colors in proportions of'between 1:1 to 6:1 of enamel colors to vehicle. The vitreous enamel colors generally consist of 5% to 20% of'inorganic oxide p gments and 95% to' of finely divided glass frit. The glass'frit may be lead, cadmium, antimonyor other metal borosilicates;

ALL-WAX VEHICLES FOR USE WITH VVITREQUSH ENAMEL COLORS IN PROPORTIONS SPECIFIED'f' Example 12 550 parts of vitreous enamel color (10% Ti0 pig mentground lead borosilicate glass) was heated to 2 200 C. and placed in a mixing container. 30 parts of. Carbowax 6000 (polyethylene glycol having an average molecular weight of about 6000 to 7500) and. 65v parts:

ofnormal stearyl alcohol was added to and mixed with the vitreous enamel color. The resulting molten paste was allowed to cool below 80 C., after which 5 parts of.

Alipal GB-SZO (a product produced by Antara Che I icals and comprising ananionic surface active agent cornposed of the sodiumhydroxide alkalinized POCl reaction p product of a higher alcohol) was added, and mixed in.

The resulting paste was passed through a 3-roll mixing mill,1th'e rolls of which were maintained at a temperature face having room temperature. In the firing step to which ,7 the coated. ceramic article is submitted, when the color composition is r emelted, the screen mesh marks and any other roughness in the surface of the coated art;c'le are smoothed out to a much greater extent than with a' similar control color composition made without the anionicsurface active agent.

The procedure of Example 12 was followed with the following compositions in the proportions set forth below with similar results to those obtained by the practice of Example 12..

if Examplel3 I ts. Carbowax.60.00 (polyethylene glycol having an average molecular weight of about 6000 to 7500) 40.

Normal stearyl alcohol 55 Anionic phosphate ester product obtained from Example 1 5 Vitreous enamel color 500 Example 14 Carbowax 6000 (polyethylene glycol having an average molecular weight of about 6000 to 7500.) 20 Siponol TX? (a mixed fatty alcohol made and sold by-' American Alcolac' Corp.-C C 4 4% C C i, 92% ;,,M;P. 48 521 C.) 70; Anionic, phosphate ester product obtained from Example 2 10 it eous e ame wcolqrn 5 0,,

Example 15 Carbowax 20,000 (polyethylene glycol having an average molecular weight of 15,000 to 20.000) 25 Carbowax 1540 (polyethylene glycol having an average molecular Weight of 1300 to 1600) 15 Adol 64 (a mixed fatty alcohol made and sold by Archer-Daniels-Midland Corp. and containing:

C 24.3%-C 68.6%C 7.1%) 55 Anionic phosphate ester product obtained from Example 3 5 Vitreous enamel color 500 Example 16 Carbowax 4000 (polyethylene glycol having an average molecular weight of 3000 to 7000) 50 Dytol 13-46 (a fatty alcohol made and sold by Roehm & Haas Company and containing: C

1.2%C 34.7%C 64.8%) 48 Anionic phosphate ester product obtained from Example 4 2 Vitreous enamel color 500 Example 17 Carbowax 6000 (polyethylene glycol having an average molecular weight of 6000 to 7500) 40 Stearyl alcohol 45 Anionic phosphate ester product obtained from Example 5 l Vitreous enamel color 450 Example 18 RESIN-WAX VEHICLES FOR USE W'ITH VITREOUS ENAMEL COLORS IN PROPORTIONS SPECIFIED Example 19 45 parts of Staybelite (hydrogenated rosin produced by Hercules Powder Company), 45 parts of stearyl alcohol, and parts of ethyl cellulose were mixed at approximately 100" C. until dissolved. The mixture was then cooled to solidify the same and broken into lumps and transferred to a container with 550 parts of vitreous enamel color and heated to a temperature of 200 C. After the mass was molten, it was mixed thoroughly and allowed to cool to 80 C. at which temperature 5 parts of Alipal 613-520 (a product produced by Antara Chemicals and comprising an anionic surface active agent composed of the sodium hydroxide alkalinized POC1 reaction product of a higher alcohol) was added, stirred in and the mass roll milled. The resultant vitreous enamel color composition is outstanding in every respect for stencil screen application onto ceramic or metal surfaces. The color composition was found to have the requisite viscosity and had the property of freezing rapidly on contact with surfaces at room temperature. In firing the coating on a ceramic or metal surface when the color composition is remelted, screen mesh marks retained thereon or other roughness of the surface of the coating were smoothed out to a much greater extent than with a control color composition made without the anionic phosphate ester.

The following examples disclose proportions of materials therein set forth which were mixed in accordance desirable vitreous enamel color compositions.

Example 21 Rosin 50 Normal stearyl alcohol 40 Anionic surface active agent prepared by Example 7 10 Vitreous enamel color 450 Example 22 Hydrogenated rosin 15 Rosin 30 Paraffin (melting point 65 30 Stearyl alcohol l5 Ethyl cellulose 2 Anionic surface active agent prepared by Example 8 8 Vitreous enamel color 550 Example 23 Carbowax 6000 (polyethylene glycol having an average molecular weight of 6030 to 7500) 20 Ethyl cellulose 5 Stearyl alcohol 70 Anionic surface active agent prepared by Example 9 5 Vitreous enamel color 400 The thermofluid vehicles of the present invention may be produced with uniform characteristics from batch to batch and, when contained in vitreous enamel color compositions and applied on a ceramic or metal surface in one or a plurality of layers of different colors, the vitreous enamel may be molten, and the color compositions will have a self-smoothing character without danger of running on the surface from the design in which they are stencilled thereon. By reason of the presence of the anionic surface active agents of this invention, it is possible to incorporate large proportions of vitreous enamel colors without producing undue viscosity of the resultant paste. In all cases, the color compositions of the present invention may be extruded through screen stencils for prolonged periods of time to give clear-cut, glossy, sharp designs.

Reference in the specification and claims to parts, proportions and percentages, unless otherwise specified, refers to parts, proportions, and percentages by weight.

Since it is obvious that many changes and modifications can be made in the above-described details without departing from the nature and spirit of the invention, it is to be understood that the invention is not to be limited to said details except as set forth in the appended claims.

I claim:

1. A thermofluid vehicle for vitreous enamel color compositions, self-smoothing and non-running at enamel fusing temperatures, consisting essentially of a substance selected from the group consisting of thermofluid resinwax vitreous enamel color vehicles and thermofluid allwax vitreous enamel color vehicles and an anionic surface active agent selected from the group consisting of neutral and alkaline reaction products of POCl and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and reaction products of POCl and both a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having a least 4 carbon atoms between the carbon atoms to which the hydroxyl radicals are attached, said resin-wax vehicle being composed of a thermoplastic resin, a wax, and a solvent for said resin and wax and said all-wax vehicle being composed of amixture of polyethylene glycol having an average molecular weight of between 3,000 and 7,500

and a saturated monohydroxy aliphatic alcohol of betweer1 l2 and 18 carbon atoms.

2. A; thermofluid. vehicle for. vi treous ,enamel color, compositions, self-smoothing and non-running at enamel usi t mn ra ur o ist n sentia l of u t c e e ed om. heeroun. con i in cf mm resinwax vitreous enamel. color vehicles and thermofluid allwax vitreousenamel color vehicles and between 0.5 and 15% of an anionic surface active agent selected from the group consisting of neutral and alkaline reaction products of POCl and ,aflsaturated monohydroxy aliphatic alcohol havingfi to 18 carbonatoms and reaction prodnets of POOl 'and both a saturated monohydroxy alipha c coh t avin r ,tqlr8s aib n t s and a i-- 3..A thermofluid vehicle for vitreous enamel color compositions, selfsmoothing and non-running at enamel fusing temperatures, consisting essentially of a thermofluid resin-wax vitreous enamel color vehicle and an anionic surface active agent selected from the group oonsisting of neutral andalkaline reaction products of POCl and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms, and reaction products of POClg and both the saturated 'mon'ohydr oxy aliphatic alcohol having 8 to 18-carbon atoms and an aliphatic glycol having at least4 carbonatoms, between the carbon atoms to which the hydroxyl radicals are attached, said resin-wax vehicle being composed. of a thermoplastic resin, a wax, and a solvent for said resin and wax.

4. thermofluid vehicle for vitreous enamel color compositions, self-smoothing and non-running at enamel fusing temperatures, consisting essentially of a thermofluid all-wax vitreous enamel color vehicle and an anionic surface, active agent selected from the group consisting of neutral and alkaline reaction products of POCl and'a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and reaction products of F001;, and 7 both thefsaturate'd inonohydroxy aliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having at least 4 carbon atoms between the carbon atoms to which the hydroxyl radicals are attached, said all-wax vehicle being composed of a mixture of polyethylene glycol having an averagemolecular weight of between 3000 and 7,500 and a saturated monohydroxy aliphatic alcohol of between 12 and 18carbon atoms.

5. A thermofluid vehicle for vitreous enamel color compositions, self-smoothing and non-running at enamel fusing temperatures, consisting essentially of a substance selectedfro-m thegroupconsisting of thermofluid resinwa'x' vitreous enamel color vehicles and thermofluid allwax vitreous enamel color vehicles and an anionic surfaceactive agent selected from the group consisting of alkali metal hydroxide and amine alkalinized reaction products of POl and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and reaction products of POCl and both a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having at least 4 carbon atoms between the carbon atoms to which the hydroxyl radicals are attached, said resin-wax vehicle being composed of a thermoplastic resin, a wax, and a solvent for said resin and wax, and said all-waxvehicle being composed of a mixture of polyethylene glycol having an averagemolecular weight of between 3,000-and 7,500 and a saturated monohydroxy aliphatic alcohol of between 12 and 18 carbon atoms.

6. A thermofluid vehicle for vitreous enamel color compositions,self-smoothing and non-running at enamel fusing ,temperatures,, consisting. essentially of a substance selected from the group consistingof thermofluid resinwax vitreous enamel, colon vehicles. and.;thermoflurd ;al l= wax vitreous enamel color vehicles and -an amqnicsurface activeagent e e ed .fwm t e rowisti t f; kalimet hydr de an? t r i mine lka inized reac products ,of QCl and a saturated :monohydroxy =5 phatic alcoholhaving 8 to 18 carbon atoms andreaction products of POCl and both a saturated monohydroxy aliphatic alcohol having-81o 18 carbon atoms andtana aliphatic glycol having at least 4 carbon atoms. between the carbonatoms to which the hydroxyl, radicals are at-V-V tached, said resin-wax vehicle being composed of a thermoplastic resin, a wax, and a solvent for said resin and wax, and said-all-wax vehicle being composed of a-mixture of polyethylene, glycol having anaverage molecular weight of between 3, 000 and 7,500 and a saturated mor1 o hydroxy aliphatic; alcohol of, between 12 and:18 carbon atoms.

7. Aihthermofluid vehicle for vitreous enamel color z,

q qsi iqn ll lfamqq hinsand n n-ru n n at me u in .tem a ures... ons stin e t l f a h tmo:

plastic resin, a wax, and a solvent for said resin and wax and a tertiary amine alkalinizedreaction product of P001 v and a saturated monohydroxy aliphatic alcohol having 8 to '18 carbonv atoms:

8. A thermofluid vehicle for vitreous enamel color; compositions self-smoothing and non-running .at enamelfusing temperatures, consisting essentially of a thermoplastic 'resin, a wax and a solvent forsaid resin and wax-.1

and a tertiary amine alkalinized reaction product of POCl and both a saturated monohydroxytaliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having atleast 4 carbon atoms between the carbon atoms to I which the hydroxyl radicals are attached."

9. A vitreous enamel color composition, self-smooth: ing and non-running at enamel fusing temperatures cone sisting essentially of a finely divided vitreous enamel color, a substance selected from the group consisting of '1 thermofluid resin-wax vitreous enamel color, vehicles and thermofluid all-wax vitreous enamel color vehicles and" an anionic surface active agent selected from the group consisting of neutral and alkaline reaction products of 10. A vitreous enamel color composition, self -smoothing and non-running at enamel fusing temperatures con-' sisting essentially of;-.a finely divided vitreous enamel; color, a substance selectedfrom the group consisting of, thermofluid resin-wax vitreous enarnel color vehicles;and thermofluid all-wax vitreous enamel color'vehicles and, between-0.5 and 15% of an anionic surface active-agent selected from the group consisting of neutral and alkaline reaction products of POCl and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and re-q. action ,products of POCl andboth a saturated monohya droxy aliphatic alcohol having 8 to 18 carbonatomsandw an aliphaticglycol having at least 4 carbon atoms be-, tween the carbon atoms to whichthe hydroxyl radicals;

are attached.

11. A vitreous enamel color-composition, self-smooth ing and, non-running at enamel fusing temperatures, consisting essentially of a finely divided vitreous enamel color, a thermofluid resin-wax vitreous enamel color vehicle, and a substance selected from the group consisting of neutral and alkaline reaction products of POCl and the hydroxyl radicals are attached, said'resin-wax ve hicle being composed of a thermoplastic resin, a wax, and a solvent for said resin and wax.

12. A vitreous enamel color composition, self-smooth ing and non-running at enamel fusing temperatures consisting essentially of a finely divided vitreous enamel color, a thermofluid all-Wax vitreous enamel color vehicle, and a substance selected from the group consisting of neutral and alkaline reaction products of F001;, and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and reaction products of PCl and both the saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having at least 4 carbon atoms between the carbon atoms to which the hydroxyl radicals are attached, said all-wax vehicle being composed of a mixture of polyethylene glycol having an average molecular weight of between 3000 and 7500 and a saturated monohydroxy aliphatic alcohol of between 12 and 18 carbon atoms.

13. A vitreous enamel color composition, self-smoothing and non-running at enamel fusing temperatures, consisting essentially of a finely divided vitreous enamel color, a substance selected from the group consisting of thermofluid resin-wax vitreous enamel color vehicles and thermofluid all-wax vitreous enamel color vehicles and an anionic surface active agent taken from the group consisting of alkali metal hydroxide and amine alkalinized reaction products of POC1 and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and reac tion products of POC1 and both a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having at least 4 carbon atoms between the carbon atoms to which the hydroxyl radicals are attached.

14. A vitreous enamel color composition, self-smoothing and non-running at enamel fusing temperatures, consisting essentially of a finely divided vitreous enamel color, a substance selected from the group consisting of thermofluid resin-wax vitreous enamel color vehicles and thermofluid all-wax vitreous enamel color vehicles and an anionic surface active agent selected from the group consisting of alkali metal hydroxide and tertiary amine alkalinized reaction products of POCl and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and reaction products of POCl and both a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having at least 4 carbon atoms between the carbon atoms to which the hydroxyl radicals are attached.

15. A vitreous enamel color composition, self'smoothing and non-running at enamel fusing temperatures, consisting essentially of a finely divided vitreous enamel color, a thermoplastic resin, a wax, and a solvent for said resin and wax, and a tertiary amine alkalinized reaction product of POCl and a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms.

16. A vitreous enamel color composition, self-smoothing and non-running at enamel fusing temperatures, consisting essentially of a finely divided vitreous enamel color, a thermoplastic resin, a wax and a solvent for said resin and wax, and a tertiary amine alkalinized reaction product of F001,, and both a saturated monohydroxy aliphatic alcohol having 8 to 18 carbon atoms and an aliphatic glycol having at least 4 carbon atoms between the carbon atoms to which the hydroxyl radicals are attached.

References Cited in the file of this patent UNITED STATES PATENTS 2,005,619 Graves June 18, 1935 2,190,210 Kaber Feb. 13, 1940 2,318,803 Schneider et al May 11, 1943 2,607,701 Jessen Aug. 19, 1952 2,607,702 lessen Aug. 19, 1952 2,617,740 Morris Nov. 11, 1952 2,656,372 Ernest et a1. Oct. 20, 1953 2,682,480 Andrews June 29, 1954 2,823,138 Hofiman Feb. 11, 1958 FOREIGN PATENTS 669,987 Great Britain Apr. 9, 1952 552,719 Great Britain Apr. 21, 1943 452,508 Great Britain Aug. 24 1936 

1. A THERMOFLUID VEHICLE FOR VITREOUS ENAMEL COLOR COMPOSITIONS, SELF-SMOOTHING AND NON-RUNNING AT ENAMEL FUSING TEMPERATURES, CONSISTING ESSENTIALLY OF A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF THERMOFLUID RESINWAX VITREOUS ENAMEL COLOR VEHICLES AND THERMOFLUID ALLWAX VITREOUS ENAMEL COLOR VEHICLES AND AN ANIONIC SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF NEUTRAL AND ALKALINE REACTION PRODUCTS OF POCL3 AND A SATURATED MONOHYDROXY ALIPHATIC ALCOHOL HAVING 8 TO 18 CARBON ATOMS AND REACTION PRODUCTS OF POCL3 AND BOTH A SATURATED MONOHYDROXY ALIPHATIC ALCOHOL HAVING 8 TO 18 CARBON ATOMS AND AN ALIPHATIC GLYCOL HAVING AT LEAST 4 CARBON ATOMS BETWEEN THE CARBON ATOMS TO WHICH THE HYDROXYL RADICALS ARE ATTACHED, SAID RESIN-WAX VEHICLE BEING COMPOSED OF A THERMOPLASTIC RESIN, A WAX, AND SOLVENT FOR SAID RESIN AND WAS AND SAID ALL-WAX VEHICLE BEING COMPOSED OF A MIXTURE OF POLYETHYLENE GLYCOL HAVING AN AVERAGE MOLECULAR WEIGHT OF BETWEEN 3,000 AND 7,500 AND A SATURATED MONOHYDROXY ALIPHATIC ALCOHOL TO BEBETWEEN 12 AND 18 CARBON ATOMS. 